The reaction of poly(vinyl chloride) containing N-methyl-N-carboxymethyl dithiocarbamate (PSDC) with metal ions in a heterogeneous system and the effects of γ-irradiation on the reactivity were studied. Slurried PSDC has an affinity for a number of metal ions in aqueous solutions. On the basis of analyses for nitrogen and sulfur and on infrared spectra, a possible chelating structure for PSDC was deduced. The gaseous products evolved during the gamma radiolysis of PSDC under vacuum were measured. Although the dithiocarbamate group bonded to the main chain gave some protection against the dehydrochlorination of poly(vinyl chloride) component, a small amount of the carboxymethyl group was decomposed. It was found that with γ-irradiation doses up to 30 Mrad, only about 1 mole-% out of 17.6 mole-% of N-methyl-N-carboxymethyl dithiocarbamate in the polymer was decomposed. It was shown that the reactivity of the irradiated PSDC in water toward metal ions was almost the same as that before irradiation.